Multiconfiguration pair-density functional theory investigation of the electronic spectrum of MnO4−
Abstract
The electronic spectrum of permanganate ions contains various highly multiconfigurational ligand-to-metal charge transfer states and is notorious for being one of the most challenging systems to be treated by quantum-chemical methods. Here we studied the lowest nine vertical excitation energies using restricted active space second-order perturbation theory (RASPT2) and multiconfiguration pair-density functional theory (MC-PDFT) to test and compare these two theories in computing such a challenging spectrum. The results are compared to literature data, including time-dependent density functional theory, completely renormalized equation-of-motion couple-cluster theory with single and double excitations, symmetry-adapted-cluster configuration interaction, and experimental spectra in the gas phase and solution. Our results show that MC-PDFT accurately predicts the spectrum at a significantly reduced cost as compared to RASPT2.
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Mar 26, 2018
- Source ID
- 10.1063/1.5021185
Entities
People
- Donald Truhlar
- Laura Gagliardi
- Prachi Sharma
Organizations
- United States Air Force
- University of Minnesota Supercomputing Institute